摘要
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Treatment of the chloro(fulvalene)zirconium(III) compound [Zr(eta~5-C_5H_5)(mu-Cl)]_2[mu-(eta~5,eta~5-C_(10)H_8)] with an equimolar amount of azobenzene in toluene,under extremely anhydrous conditions,gives the mu-[bis(iido)] deri...
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Treatment of the chloro(fulvalene)zirconium(III) compound [Zr(eta~5-C_5H_5)(mu-Cl)]_2[mu-(eta~5,eta~5-C_(10)H_8)] with an equimolar amount of azobenzene in toluene,under extremely anhydrous conditions,gives the mu-[bis(iido)] derivative [Zr(eta~5-C_5H_5)(mu-NPh)]_2[mu-(eta~5,,eta~5-C_(10)H_8)](1).However,when this reaction is carried out under insufficiently dry conditions a mixture of the previously reported mu-oxo complex [Zr(eta~5-C_5H_5)(mu-Cl)]_2(mu-O)[mu-(eta~5,eta~5-C_(10)H_8)] and 1,2-diphenylhydrazine is obtained.When the chloro(fulvalene)zirconium(III) compound reacts with benzo[c]cinnoline the mu-(eta~2,eta~2-N,N-hydrazdo)complex [Zr(eta~5-C_5H_5)(mu-Cl)]_2[mu-(NC_6H_4C_6H_4)][mu-(eta~5,eta~5-C_(10)H_8)](2a) is obtained,which rearranges to the thermodynamically more stable 2b.Addition of an equimolar amount of RNC (R=nBu,C_6H_(11) to a toluene solution of [Zr(eta~5-C_5H_5)(mu-Cl)]_2[mu-(eta~5,eta~5-C_(10)H_8)] gives [Zr(eta~5-C_5H_5)(mu-Cl)]_2[(mu-CNR)(eta~5,eta~5-C_(10)H_8)] [R=nBu(3),C_6H_(11)(4)].Reaction of [Zr(eta~5-C_5H_5)(mu-Cl)]_2[(mu-CNtBu)[Mu-(eta~5,eta~5-C_(10)H_8)] with 1 equiv.of PhCH_2MgCl or (PhCH_2)_2Mg(THF)_2 afforded the monobenzyl derivatives [Zr(eta~5-C_5H_5)(CH_WPh)(Cl)](muCNtBu)[Mu-(eta~5,eta~5-C_(10)H_8)] (5 and 6).When this reaction was carried out with 2 equiv.or an excess of PhCh_2MgCl,a mixture of themonobenzyl and dibenzyl compounds [Zr(etaC_5H_5)]_2(CH_2Ph)(Cl)(mu-CNtBu)(mu-eta~5-eta~5-C_(10)H_8)] (5) and [Zr(eta~5-C_5H_5)(CH_2Ph)(Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] (5) and [Zr(eta~5-C_5H_5)(CH_2Ph)(Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] (7) is obtained.Similar reactions with 1 or 2 equiv.of (CH_E)_3SiCH_2Li afford a mixture of the monoalkyl and dialkyl compounds [Zr(eta~5-C_5H_5)(CH_2Si)(CH_3)_3](Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] (8)and(eta~5-C_5H_5)(CH_2Ph)(Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)[Zr(eta~5-C_5H_5)(CH_2Si)(CH_3)_3](Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] (9) compounds.Moreover,methylationof [Zr(eta~5-C_5H_5)(Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] gives the analytically pure tetramethyl derivative [Zr(eta~5-C_5H_5)(CH_2Si)(CH_3)_3](Cl)(mu-CNtBu)[mu-(eta~5,eta~5-C_(10)H_8)] (10),whereas [Zr(eta~5-C_5H_5)(CH_2Si)(CH_3)_3](Cl)(mu-CNC_6H_(11) [mu-(eta~5,eta~5-C_(10)H_8)] reacts with MeLI togive a mixture of the monomethyl derivatives [Zr(eta~5-C_5H_5)(CH_3)_3](Cl)(mu-CNC_6H_(11))[mu-(eta~5,eta~5-C_(10)H_8)] (11 and 12),as well as the dimethyl compound [Zr(eta~5-C_5H_5)(CH_2Si)(CH_3)_3](Cl)(mu-CNC_6H_(11)[mu-(eta~5,eta~5-C_(10)H_8)] (13).
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